Method for extracting pigments



April zo, 194s. J. IM. TABOR fr AL .2,440,029 METHOD FOR EXTRACTING PIGMENTS Filed 0G13. v13a, 1943 Patented Apr. 20, 1948 .METHOD EGR EXTRAC1'1IN ,G :PIGMENTS Joseph M. Tabor, Cleveland, -and Howard F. ASeibert. and flaul TRAP-'ro hring,-ChagringFalls, Ohio,

assignors 'to 'General Biochemicals, Inc., `1Chagrin-Falls, zhio, a corporation of :Ohio

Applicationoctobcr 13, 1943, Serial No. 506,060

This invention relatesfto a `method and apparatus for extracting pigments, includingspecically carotene, and carotinod pigments, from fatty materials, such, for example, --as animal or vegetable oils .andfa'ts r An object of "the -invention is :to provide a simple and efii-cientapparatus and lmethod for extracting pigments including vplant pigments.

Another .object .is lto provide practical, commercial vapparatus comprising a .closed -uid system.

Another object of the'inventionisto=provde a process of .extracting vpigments Vwhich is vWell adapted: to protect the Ypigment. or. pigments vfrom decomposition ,during the performance of the process.

Another object of fthe invention `is Ato-provide a method of ithe labove `mentioned 'kind all the steps ofwhich maybe v'performed'in a-singlevesstel, thereby eliminating expensive :.grinding, drying and transferringfequipment.

A ,further object `-of the :invention :is to .provide Vsuch-a :process in the-carrying out of `.which soap ;is produced as ;a-val.uable by-fproduct.

@ther objects will tbe in part `obvious vor 'in part pointed out hereinafter.

Thefinvention accordingly yconsist-sA in #the ifeatures fof zconstruction, `combinations of elements, arrangements of parts,l Aand in stherseveral steps and ,relationand ,order :of :each of :said steps @to one orf-more ofvtheothers'thereof, all .as=wi11be pointed :out in the :following description, and the scope` of :the application :of .which :.willbe rindicated in :the following; claim.

The accompanying drawing is ra rront,releva tion showing. 'diagrammatically apparatus .for Carrying outxfthe invention.

In :carrying ,out-our invention we provide the vessel in which Aal1 steps of --the therein fdc--v scribedmethodrare performed, Vand' connect .vessel :lo ,with lthe container -lsl' A.-vvli-ich contains lthe material fflomf :which Ithe *.pigment is A:to fbe -extratednby conduit .ft-2; having therein valve |3; with thecontainerilfd fora saponifyingagentfby condui t5 .which rhasthereinvalve t I6', .and which mayqdischarge intoconduit .t2 between valve and' vessel fritas fillustratedherein; .with vacuum pump itl through vacuum Aline l, having- :the branch `line its, in which valve i211 :is provided,

and .which l'eadstovacuumcondenser i2f| which is connected. vby conduit ,22 to the :dust :trap 23, which iin :turn is connected 4with the -vessel Elil throughvaportline :24; with the solvent storage tank fthroughconduit 43, whichihas therein the valve 4;4; .and leads to.:solvent pump 28, :and

`2 through 'line 2.9 which branches off from line 28, 'through valve l311; `and with extract tank 3l through line 32, which'has therein valve 33, and line sight s, and communicates with extract pump 34, andithrough line 31, which hastherein valve 38;

A receiver tank v39 is provided"interconnected with vacuum condenser 2l "by conduit 40 and interconnected with solvent storage tank 25, throughline M Whichthas the valve 4L-through solvent pump 28, 'an-dithrough line A26 which yhas therein ,valve-21.

vVacuum-pump |1-is also connected-to solvent storage 4tank 25 `tlfirouglfr exhaust vapor Vline 45 leadingito'the atmospheric condenser 46, which is connected by conduit 4-1 to thereceiver 48, which is connected -to`line-4|, through branch line 49, Vhaving"therein Yvalve 50, vthrough solvent pump `28, -and through -line 216 4which vhas -therein valve21.

The above vdescribed system lconstitutes 4the apparatus `for Ycarrying out our extraction method which IWe perform inthe single vessel I0. However, the following `further apparatus may conveniently be connected with Athis system las follows: the evaporator 45| may be Yconnected with extract tank 73| -through Vconduit '52, having Avalve 53' and 'line sight s, and branching from i'line 31 ybelow valve 38, and through extract ,10111111034 ,and through conduit 35 which has vtherein valve 35. As illustrated, conduit 5-2 is connected with evaporator 5I near its top. Atthev-bottom of evaporator -5l a discharge outlet maybe provided;indicated-bythe conduit 5 la, having in its lower vend -valve lSIb. Evaporator 5l lmaybe interconnected with solvent storage tank 7through vapor line 54 leading fromthe topof the evaporator 55|, lto atmospheric condenser -55' which in 4turn is interconnected to solvent storage ntank25 through conduit 56.

In 'addition to evaporator "5l a nishing still 51 may, if desired'be associated vwith the above described-system, -as-by vaporline 58 `leadingfrorn the Viinishing still V51 tothe vacuum condenser 5t, which in turn is connected to vacuum pump l1 yby vacuum line extension 18a, which has therein valve Gi) and is Iconnected to vacuum line i8, `and condenser 53 may lbe connected through conduit 6| -with `a receiving tank B2, which in kturn is connected to storage tank 25 through the line 63, ,having therein valve 64, through solvent pumpeZ- and line 26.

There lis thus provided a closed system, lwhich may be exclusive of 'evaporator 5l and vfinishing Still 51 and their connections to the remainder of the system, by means of which all of the steps of our extraction process may be performed as will now be described.

We first start vacuum pump I'I, which as stated above, is connected with vessel ID through conduits I3 and i9, condenser 2I, conduit 22, dust trap 23 and vapor line 2,4. We draw into vessel Iil, Aas by means of the partial vacuum maintained therein by vacuum pump I1, the raw material from which the pigment is to be extracted, which, for the purpose of exemplification, may consist of a source of carotinoid pigments, such, for example, as melted palm oil, supplied from tank II through conduit I2. order to supply the palm oil to vessel III valve I3 is of course initially opened and is closed when the desired volume of palm oil has been discharged into vessel I0.

It will of course be understood that in a like manner, when communication is desired between vessel Ill and any of the elements of the system, the valve means for the element, described above, will be utilized to control the flow to or from vessel It.

We next similarly draw into vessel Ill from tank I4, through conduits I5 and I2, after closing valve I3 and opening valve I6, an amount of a fty percent aqueous caustic alkali which is chemically Vequivalent. to, or preferably somewhat in excess of, the amount of melted palm oil drawn into vessel Ill. The caustic alkali reacts with the oil causing saponication of the oil, asis well understo-od in the art, and we preferably promote this reaction by maintaining agitation in the vessel ID during the entire saponication period. Preferably vessel I0 is an agitator and rotary drier of the spiral conveyor type the blades of which are set as close Ato the shell as possible.

The saponiiication reaction steps release an amount of heat suflicient to heat the soap as it is formed, in which a substantial amount of pigment material is entrapped, to vaporize the moisture in the newly formed soap lumps thus disintegrating them, and to raise the temperature in a container at atmospheric pressure to a degree which promotes rapid decomposition of the pigment being extracted. During this step and also succeeding steps we protect the pigment being extracted from such decomposition. We accomplish this by lowering and regulating the temperature in vessel I0 by controlling the degree of vacuum in vessel I0. The degree of vacuum necessary can be estimated from the decomposition point of the material which it is desired to extract. Thus, for example, carotene decomposes rapidly at temperatures above 80 C. Reference to standard steam tables shows that water boils at this temperature under a pressure of 355 mm. of mercury. Accordingly, the saponication pressure for carotene-bearing oils should not be allowed to exceed v355 mm. for any substantial period; since aqueous solutions under a given pressure boil at higher temperatures than water, depending on their concentrations, the saponincation pressure is preferably kept lower than this.

The employment of reduced pressures has the further advantages that it results in the exclusion from vessel Ill of air the presence of which would be detrimental since it would promote' decomposition by oxidation of the carotene or other pigment being extracted, and facilitates the breaking down of newly formed soap lumps and the consequent freeing therefrom, and the recovery of, pigment containing material.

Depending upon the characteristics of the pars ticular kind of material or oil to be treated we have found, as stated above, that it is sometimes desirable to'employ somewhat more of the alkali solution than is required to provide an amount which is the exact chemical equivalent of the amount of the oil or other fatty material being treated. We have found that certain oils have a tendency to form a soft soap, and that a harder soap, and one having better powdering characteristics, m-ay be obtained by using an amount of alkali solution which is greater than the chemical equivalent of the particular oil or other fatty material being treated, the increased amo-unt, over and above the chemical equivalent amount, being determinable by experimentation in each case. Thus, for example, we have found that in the treatment of palm oil we obtain very satisfactory results employing twenty percent more of the aforesaidfty percent aqueous caustic alkali than is necessary for chemical equivalen-cy with the amount of palm oil being treated.

During the, saponification step the amount of heat evolved is sufficient to flash off the water in which the alkali was dissolved. 'The water vapor is withdrawn through vapor line 24, dust trap 2,3, and line 22, into condenser 2l' where it is condensed, and may be drawn olf, through an outlet, not shown, and discarded, when the saponication step is completed. The resulting soap is then in a very dry and finely powdered mass which requires no further processing before the pigment is extracted.

Saponification proceeds as soon as contact .between the oil and the alkali is made, and the alkali should be distributed as evenly as possible throughout the oil because, if even distribution is not obtained, heavy ballsof soap may form which will cause serious trouble. For this reason we prefer to provide one or more windows w in the dome cover cof vessel I0 through which the operator may watch the reaction closely, and if he observes any tendency of the mixture to foam he should release the vacuum momentarily, as by opening vacuum release Valvev Ib which Vcommunicates with the interior ofv vessel I9 through line Illa.

Performing the saponirlcation step under vacuum contributes to the rapid elimination of steam from the soap mass', thereby reducing the lumps which ordinarily form during the saponication step, producing a very unexpectedly ne dry powder. In previous methods employed the soap was not completely powdered and the pigment entrapped in the lumps or unpowdered portion of the soap was lost.. Y

When the saponication step is complete and the soap has been completely powdered, agitation within vessel Ill is discontinued and a solvent, such, for example, as one of a group comprising benzene, nitrobenzene, ethylene dichloride, and petroleum ether, is drawn directly into the vessel I0 from the solvent storage tank 25 through conduits 43 and 29, as described above. Enough solvent is added to bring the levell thereof, in vessel I0, up to the top of the agitator means employed, which is not shown but which, as stated above, is preferably of the' spiral conveyor type with the blades set as closely as possible to the shell of the vessel. The vacuum at this time is discontinued and agitation is recommenced and continued for approximately fteen minutes or until the soap is thoroughly wetted. When the solvent and soap have been intimately mixed agitation is discontinued and the SOap and the extract bearing solvent are al.

aandoen:

lowedtoseparateqby gravity. The: .clear-extract: bearing: solventi-is: drawn@- ofrii intocthe extracn storage: tank 33| :througmconduitsf 32 :and'31l: and;

been drawn out of vessel III,I fresh-.1solvent`v foll another wash may be drawn into vessel IIJ, in the manner set forthV above,` and: agi-tation is resumedfor approximately fteen minutes til ,the remaining. `seanis .again thorouehly:v vetteslz'- with-solventaiter which the agitation isstopneds theV soap-and the extratbearing solventrare again allowed toV separate, .andi-amer separation. thev extract bearing solventy isf-drawn oiagain; as described rabove.

The extracting step may be-repgeatediinllthis Way as many times as economy" of time; and material permit.

After the additional ,washingg steps, whichccrn- T prise reintroducingsolvent, mixing it Withthe soap in vessel I0, separating the soap and the extract bearing solvent, and separately Withdrawing the extract bearing solvent, have been repeated the desired number of times, the vacuum pump I1 is started again and the vacuum condition within vessel is restored and the soap is. dried under vacuum. When the solvent stops distilling from the soap, dry steam is introduced into vessel l0, through an inlet not shown, and the last traces of solvent are removed from the soap by steaming for a short period, on the order of live minutes, while under vacuum, thereby further drying the extracted soap. 'I'he solvent separated by the steaming step is recovered in the vacuum and atmospheric condensers 2| and 4'6 respectively from which it is returned to solvent storage tank 26 as described above.

During the step of drying the soap remaining in drier I0 after the last wash the operator should be on guard to detect and prevent foaming and should momentarily release the vacuum in vessel Ill by opening vacuum release valve Illa if foaming occurs.

After the extraction of the pigment from the oil, as described above, has been completed, the soap, which is powdered and substantially pigment free, is removed from vessel I0, and the cycle of treatment in vessel l0 is complete. A new batch of oil may now be drawn into vessel l and the cycle repeated.

If it is desired to concentrate the extract collected in storage tank 26 it may be pumped into evaporator through conduit 52 after opening valves 35 and 53 in lines 35 and 52 respectively and closing valves 33 and 33 in lines 31 and 32 respectively. Care should be taken to prevent any soap from coming into the evaporator 5|. Any soap which may have gotten into tank 3| will separate by gravity and the extract may then be decanted from tank 3|. Any soap which has found its way into tank 3| may therefore be vretained therein and returned to vessel I0 in the first wash of the flollowing batch of material being treated.

After concentration in evaporator 5| the extracts may be withdrawn, as by opening valve 5|b, and cooled. At this stage the extracts will retain a certain amount of soap which we vlter out, as for example, by the use of Buchner funnels using a liberal amount of lter aid, and we thereafterx washf the: resultingn filter. cake thoroughly with Afresh lsolvent'andtransfer the combining'.dltrates'-into-V I'lnishingustill 5T- where a iinal concentration step may be performed under e, vacuum, drawn by vacuum pump- |1 through vacuumy lines |8 and1-|8'a,. as by steam distillin'g saidr'ltratesf.y withv dry steam introduced into still 5'|'by=an inlet not. shown, for vabout ve minutes toremove the-last traces ofv solvent. Vapor released during. this step is. Y removed throughI vapor line.l5& to the vacuum condenser 595 from whichl the recovered'l solvent is discharged into-.receiver 52, from which it may be returneortcA solventstorage tank` 25` through returnlir1ef:|i3,` as 1 described' above.`

Theiinaliconcentr-ate maybe withdrawn from stilllfth'roughan1outlet conduit 51a controlled by. valve-'5161. The-extractfat this point should beahandledvery: carefully since excess heat and the@containers-being completely lled so as. to.

leave;:.the: minimum v,possible air space, and nitrogen.shouldwbebubbledvthrough .the solution to iny sure complete displacement of air jlust before sealing. v

We have found that in treating 1000` lbs. of melted palm oil, in the apparatus and according to the method described above, the soap formed by the reaction of the oil `and alkali will start to crumble in `about twenty minutes after the alkali has been added, and will be completely pulverized after about an hour and fteen minutes. The reduced pressure employed within vessel I0, together with the heat of reaction of the saponifying step creates a great temperature diiferential between the inside and the outside of the soap lumps and the vaporizing of the internally contained water vapor breaks up or explodes the lumps While they are hot and readily breakable, thus freeing an amount of pigment which may represent as much as twenty percent of the total yield. For each solvent wash approximately fteen minutes is required until the soap is thoroughly wetted. The step of drying the soap,forrmed as a by-product of the extraction, requires on the order of four hours when using in vessel I9 `a vacuum of approximately 26 inches of mercury, roughly a pressure of 100 mm. The over-al1 time required for the treatment of 1000 lbs. of palm o'il from start to nish is about fourteen and a half hours.

One operator can readily control and carry out the operation of the system. During the drying period he may, if desired, use his time for iltering the extracts, after they have been concentrated in evaporator 5|, say to approximately ten gallons for -a batch of 1000 lbs. of palm oil.

The over-al1 yield of pigment obtained is high, being from to 90% in the case of carotene extracted from palm oil. This result is due in large part to the reduction of lumps of soap, as explained above, thus permitting the pigment contained in the lumps to be freed and recovered instead of being lost.

It will thus .be seen that there has been provided by this invention a method, apparatus, and an article in which the various objects hereinabove set forth together with many thoroughly practical advantages are successfully achieved. As various possible embodiments might be made of the mechanical features of the above invention, and as the art herein described might be varied in various parts, all without departing from the scope of the invention, it is to be understood that all matter hereinbefore set forth or shownin the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.

What we claim is: Y

In a process of extracting a heat-sensitive pigment from a pigment-containing saponifiable fatty material, the steps which comprise: reacting said fatty material Vwith an aqueous saponifying agent, agitating the mixture, comminuting the resulting soap by exhausting gases and vapors from the reaction zone to reduce Athe pressure therein and utilize the heat of saponication `to fboil and thus evaporate Water dispersed throughout the soap mass, the reduction in pressure lbeing such as to ensure a boiling temperature not above the decomposition point of the pigment, said temperature being not above 80 C., thereby disrupting and disintegrating such soap lumps as may form, continuing the evaporation under a partial vacuum effective to maintain a temperature not above -the decomposition point of the pigment long enough to convert the soap to a substantially dry, finely divided 8 soap mass, and extracting pigment Ifrom said finely divided mass with an organic solvent for said pigment which is a non-solvent for said soap.

JOSEPH M. TABOR. HOWARD F. SEIBERT. PAUL R. FROHRING.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date Re. 20,772 Clayton June 28, 1938 2,136,030 Stoni Nov. 8, 1938 2,170,872 Peebles Aug. 29, 1939 2,245,536 Thurman June 10, 1941 2,266,830 Taylor et al Dec. 23, 1941 2,271,406 Thurman Jan. 27, 1942 2,318,748 Buxton May 11, 1943 2,318,749 Buxton May 11, 1943 2,347,565 Kokatnur Apr. 25, 1944 2,383,630 Trent Aug. 28, 1945 2,383,631 Trent Aug. 28, 1945 Certcate of Correction Patent No. 2,440,029. i April 20, 1948. JOSEPH M. TABOR ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requuing correction as follows: Column 8, line 15, list of references cited, for Stoni read Stone; line 24, after 2,383,631 Trent Augf"28, 1945 add the following:

2,264,390 Levine et al Dec. 2, 1941 1,807,232 Wurster et al May 26, 1931 2,324,195 Carlson et al July 13, 1943 1,690,091 Marcus Oct. 30, 1928 2,031,991 Ungnade et al Feb. 25, 1936 Y OTHER REFERENCES Publication: Chemistry and Physiology of the Vitamins, Rosenberg. Interscience Publishers, Inc., New York, 1942, page 43.

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oice.

Signed and sealed this 13th day of July, A. D. 1948.

THOMAS F. MURPHY,

Assistant onumasoner of Patents. 

